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利用多种路径积分策略计算量子硬球流体的状态方程。

Computation of the equation of state of the quantum hard-sphere fluid utilizing several path-integral strategies.

作者信息

Sesé Luis M

机构信息

Departamento de Ciencias y Tecnicas Fisicoquimicas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia, Paseo Senda del Rey 9, 28040 Madrid, Spain.

出版信息

J Chem Phys. 2004 Aug 22;121(8):3702-9. doi: 10.1063/1.1776114.

Abstract

The compressibility factor of the quantum hard-sphere fluid within the region (rho(N) ()</=0.8,lambda(B) ()</=0.9) is computed by following four distinct routes involving the three pair radial correlation functions that are significant in the path-integral context, namely, instantaneous, pair linear response, and centroids. These functions are calculated with path-integral Monte Carlo simulations involving the Cao-Berne propagator. The first route to the equation of state is the instantaneous standard one, i.e., the usual volume derivative of the partition function expressed in terms of the instantaneous pair radial correlations. The other three routes stem from the extended compressibility theorem, which associates the isothermal compressibility with the three pair radial structures mentioned above and involves the solving of appropriate Ornstein-Zernike equations. An analysis of the error bars in the quantities computed is reported, and it is proven the usefulness of the centroid pair correlations to fix quantum equations of state. Also, the regions where the fluid-solid changes of phase should take place are identified with the use of indicators sensitive to order in the sample. The consistency of the current results is assessed and comparison with data available in the literature is made wherever possible.

摘要

通过四条不同路径计算了量子硬球流体在区域((\rho(N)^\leq0.8),(\lambda(B)^\leq0.9))内的压缩因子,这四条路径涉及路径积分背景下重要的三个对径向关联函数,即瞬时、对线性响应和质心关联函数。这些函数通过涉及曹 - 伯尔尼传播子的路径积分蒙特卡罗模拟进行计算。状态方程的第一条路径是瞬时标准路径,即通常用瞬时对径向关联表示的配分函数的体积导数。其他三条路径源于扩展压缩性定理,该定理将等温压缩性与上述三个对径向结构联系起来,并涉及求解适当的奥恩斯坦 - 泽尼克方程。报告了对所计算量的误差条分析,并证明了质心对关联对于确定量子状态方程的有用性。此外,利用对样本中有序性敏感的指标确定了流体 - 固体相变应该发生的区域。评估了当前结果的一致性,并尽可能与文献中的数据进行了比较。

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